Reaction products of 2, 6-bishydroxymethyl-4-phenylphenol and alkyl phenols



REACTION PRODUCTS F 2,6-BISHYDROXY- METHYL-d-PHENYLPIENOL AND ALKYL PHENOLS Frederick J. Webb, Akron, Qhio, assignor to The Firestone Tire & Rubber Company, Akron, Ohio, :1 corporation of ()hio No Drawing. Continuation of application Serial No. 520,133, July 5, 1955. This application June 11, 1959, erial No. 819,557

compounds are useful as rubber antioxidants as disclosed and claimed in my application Serial No. 520,131, filed July 5, 1955. This application is a continuation of my aplication Serial No. 520,133, filed July 5, 1955 and now abandoned.

The compounds include reaction products of 2,6-bishydroxy-methyl-4-phenylphenol and 2 ,4-dimethylphenol, 2-ethyl-4-methy1phenol, or any 2-propyl, butyl, amyl, hexyl, heptyl, octyl or nonyl-4-methylphenol.

The invention is illustrated by the following examples. In each example, 2,6-bishydroxymethyl-4-phenylpheno1 was used, and this was prepared as follows:

2,6-bishydroxymethyl-4-phenylphenol To a solution of 85 grams (0.50 mole) of 4-phenylphenol and 25 grams of sodium hydroxide in 100 ml. of water and 250 ml. of ethanol there was added 100 grams of formalin (37 percent aqueous). The reaction mixture was allowed to stand eight days at room temperature in a covered beaker and then partially evaporated at low temperature in vacuo. The yellow sodium salt which separated was filtered off, dissolved in Water, and acidified with glacial acetic acid to give 74.3 grams of a white crystalline solid. This melted to a cloudy liquid at 105110 C. after crystallization from ethyl acetate petroleum ether. For analysis, 5 grams of the product were recrystallized twice from ethyl acetate and petroleum ether, twice from acetic acid and water, and twice from ethanol and water to give a constant melting point of Ill-112 C.

Analysis.Calculated for C 4H O C, 73.00; H, 6.13. Found: C, 73.09, 72.90; H, 6.11, 6.06.

ateat O ice This recrystallized 2,6-bishydroxymethyl-4-phenylphenol was used in each of the following examples:

Example ].Reaction products of bishydroxymethyllphenylphenol and tt-octyl-4-methylphenol tion from ethyl acetate and petroleum ether gave 1.7

grams of crystals melting at -148 C. and 2.5 grams of crystals from the filtrate melting at ISO-152 C. (Cloudy.) The latter portion on recrystallization melted at 155-l60 C.; weight: 2.0 grams. This product has the foregoing general formula.

Example 2.Reacti0n product of bishydroxymethyl-iphenylphenol and 2-t-butyl-4-cres0l A mixture of 13.1 grams (0.08 mole) of 2-t-butyl-4- methylphenol and 9.2 grams (0.04 mole) of bishydroxymethyl-4-phenylphenol were dissolved in 30 ml. of warm glacial acetic acid. The solution was cooled somewhat and saturated with dry hydrogen chloride. After 8 days at room temperature, the reaction mixture was poured into 1500 ml. of water. The product separated as a white solid which was filtered off, washed free of acid with water, and dried in vacuo; weight: 20.0 grams. In a capillary tube the product softened at 80-90 C. and melted to a cloudy liquid at l18-l20 C.

The foregoing examples are illustrative. tion is covered in the claims which follow.

' What I claim is:

1. Compounds having the formula 0H 0H OH R-[ ICED-I TORT In 7 011a uHa CH:

in which R is an alkyl radical of 1 to 9 carbon atoms.

2. The compound of claim 1 in which each R is a tt-octyl group. 3. The compound of claim 1 in which each-R is a t-butyl group.

References Cited in the file of this patent UNITED STATES PATENTS 2,538,355 Davis et al. Jan. 16, 1951 2,598,234 De Groote et al. May 27, 1952 2,628,212 Young Feb. 10, 1953 2,647,102 Ambelang July 28, 1953 The inven- I 

1. COMPOUNDS HAVING THE FORMULA 